ABSTRACT
Developing porous adsorbents for efficient separation of C4 olefins is significant but challenging in the petrochemical industry due to their similar molecular sizes and physical properties. The separation efficiency is often limited when separating C4 olefins by a single separation mechanism. Herein, an ultramicroporous yttrium-based MOF, Y-dbai, is reported featuring cage-like pores connected by small windows, for recognition and efficient separation of C4 olefins through a synergistic effect of thermodynamic and kinetic mechanisms. At 298 K and 1 bar, the adsorption capacities of Y-dbai for C4H6, 1-C4H8, and i-C4H8 are 2.88, 1.07, and 0.14 mmol g-1, respectively, indicating a molecular sieving effect toward i-C4H8. The C4H6/i-C4H8 and 1-C4H8/i-C4H8 uptake selectivities of Y-dbai are 20.6 and 7.6, respectively, outperforming most of the reported adsorbents. The static and kinetic adsorption experiments coupled with DFT calculations indicate the separation should be attributed to a combined effect of thermodynamically and kinetically controlled mechanism. Breakthrough experiments have confirmed the excellent separation capability of Y-dbai toward C4H6/1-C4H8, C4H6/i-C4H8, and C4H6/1-C4H8/i-C4H8 mixtures.
ABSTRACT
At the beginning of the 21st century, the July and August (JA) mean upper-tropospheric temperature over East Asia shows a significant increasing trend, contrary to the decreasing trend in the late 1970 s. The largest warming center is over northern China (between 30°N-45°N and 85°E-120°E) around 300 hPa. Together with the temperature rising, the geo-potential height rises above the warming center and drops below, which connects closely to a correspondingly significant decadal shift of the general circulation over East Asia. In the upper-level of the troposphere, an anomalous anti-cyclone dominates, and the 200-hPa westerly jet strengthens due to the increasing pole-ward geo-potential height gradient. In the lower-troposphere, the anomalous southerly wind increases around Yangtze River Valley and the East Asian summer monsoon intensifies. The integrated circulation changes seriously impact summer precipitation over East Asia. The so-called "southern flood and northern drought" (SFND) pattern since the 1970 s over eastern China has changed. As the cooling center in the 1970 s moves southward, the dry belt moves southward as well. A wet belt dominates the Huaihe River Valley after the temperature trend reversal at 2005 while southern China experiences a dry condition.
